Detergent compositions containing reversed zwitterionicc phosphorus compounds

ABSTRACT

DETERGENT COMPOSITIONS CONTAINING REVERSED ZWITTERIONIC COMPOUNDS HAVING A NEGATIVELY CHARGED CENTER ADJACENT A HYDROPHOBIC CHAIN AND A POSITIVELY CHARGED CENTER REMOVED BY 2 TO ABOUT 4 CARBON ATOMS FROM THE NEGATIVELY CHARGED CENTER ARE DISCLOSED. THESE COMPOUNDS HAVE THE FORMULA R-Z-R1-X WHERIN R IS AN ALIPHATIC RADICAL, E.G., ALKYL OR ALKENYL, CONTAINING FROM ABOUT 10 TO ABOUT 20 CARBON ATOMS; Z IS A NEGATIVELY CHARGED RADICAL SELECTED FROM THE GROUP CONSISTING OF PHOSPHATE, PHOSPHONATE, AND PHOSPHINATE RADICALS; R1 IS AN ALKYLENE RADICAL CONTAINING FROM 2 TO ABOUT 4 CARBON ATOMS; AND X IS A POSITIVELY CHARGED RADICAL SELECTED FROM THE GROUP CONSISTING AMMONIUM AND TERIARY SULFONIUM RADICALS; SAID AMMONIUM RADICAL HAVING THE FORMULA   -N(+)(-R2)(-R3)-R4   WHEREIN R2, R3 AND R4 ARE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, METHYL, AND ETHYL; SAID TERTIARY SULFONIUM RADICAL HAVING THE FORMULA   -S(+)(-R5)-R6   WHEREIN R5 AND R6 ARE SELECTED FROM THE GROUP CONSISTING OF METHYL AND ETHYL.

252-095. Xrt 3560393 EX United States Patent ()flice Patented Feb. 2, 1971 US. Cl. 252-152 4 Claims ABSTRACT OF THE nrscLosuRn "Detergent compositions containing reversed zwitterionic colnpounds having a negatively charged center adjacent a Qtydrophobic chain and a positively charged center removed by 2 to about 4 carbon atoms from the negatively charged center are disclosed. These compounds have the formula RZR --X wherein R is an aliphatic radical, e.g., aLkgl or alkenyl, containing from about to about car n atoms; Z is a negatively charged radical selected from the group consisting of phosphate, phosphonate, and phosphinate radicals; R is an alkylene radical containing from 2 to about 4 carbon atoms; and X is a positively charged radical selected from the group consisting of amrrionium and tertiary sulfonium radicals; said ammonium radical having the formula wherein R, R and R are selected from the group consisting of hydrogen, methyl, and ethyl; said tertiary sulfonium radical having the formula wherein R and R are selected from the group consisting of methyl and ethyl.

This application is a division of US. patent application Ser. No. 584,099, filed Oct. 4, 1966, now Pat. No. 3,507,- 937, in the name of Roger B. Zimmerer and entitled Reversed Zwitterionic Phosphorus Compounds.

This invention relates to novel zwitterionic detergent compounds and to detergent compositions containing these compounds. These compounds have a negatively charged center adjacent a hydrophobic chain, and a positively charged center removed by 2 to about 4 carbon atoms from this negatively charged center. These compounds are characterized herein as being reversed zwitterionic compounds to distinguish them from more conventional zwitterionic compounds in which a positively charged center is adjacent the hydrophobic chain, and a negatively charged center is removed by two or more carbon atoms from this positively charged center.

There are several properties that are regarded as being essential for a compound to be suitable for use as a detergent. Foremost, is the cleaning ability of the compound, i.e., its ability to remove soil, e.g., from soiled clothes. In addition, the detergent should remain in active form under conditions of usage, e.g., at high temperatures such as 140 F. and in aqueous solutions. Although there are a number of organic detergents which have these properties, detergent compuonds such as those of the present invention which have additional desirable properties find wider scope of application.

The novel reversed zwitterionic compounds of this invention clean as well as,tetrapropylenebenzenesulfonate. They remain in active form during conditions ordinarily encountered during washing. In addition, they remain in atcive form when mixed jiyith builders and with anionic,

nonionic, cationic, ampholytic, and zwitterionic detergents. Moreover, anionic ighteners remain in active form when mixed with the present reversed zwitterionic detergent compounds.

The reversed zwitterionic compounds of this invention have the formula RZ R -X wherein R is an aliphatic radical, e.g., alkyl orfalkenyl containing from about 10 to about 20 carbon atoms; Z is a negatively charged radical selected from the' 'g roup consisting of phosphate, phosphonate, and phosphinate radicals; R is an alkylene radical containing from'Z to about 4 carbon atoms; and X is a positively charged radical selected from the group 'consisting of ammonium and tertiary sulfonium radicals;

said ammonium radical having the formula N R RfR wherein R, R and R are selected from the group consisting of hydrogen, methyl; and ethyl; said tertiary sulfonium radical having the-formula ggsgs wherein R and R are selected from the group consisting of methyl and ethyl. The phosphate radical herein has the formula The phosphate radical herein has the formula Q'e The phosphinate radical het ein has the formula R, R and R can be the same or different within the same molecule. R and R can be the same or different within the same molecule.

For purposes of organization and convenience the above compounds wherein R, R or R are hydrogen aretermed zwitterionics herein. These compounds might more appropriately be classified as ampholytics since they deprotonate to the extent of one hydrogen over a wide pH range, including the alkaline pH range, forming the corresponding compounds containing an aminomoeity. Thus, in detergent compositions containing water or moisture or under conditions of usage, these compounds are present in ampholytic form. They, however, may be isolated in zwitterionic form and are ordinarily in this forin at the instant of preparation of the detergent composition containing them.

Reversed zwitterionic detergent compounds, none of which are known to be described in the prior art, and exemplary of those within the scope of the present invention are set forth in Table I below wherein R, Z, R, X, R, R R R and R are applied in the formulas set forth above.

TABLE I B Z R X R R R R B' 1-. Decyl Phosphate... Ethylene Ammonlum Methyl Methyl Methyl 2... do do do .i..do d 3; 'Irimethylene. .do.

4; 'Ietramethylene ..do 5... Ethylene Tertiary sulionium 6... Tetramethylene ..do 7. E A 8. 9- 10.

ll- 12. MethyL. yl 13. do. .....do Hydrogen. Hydrogen... 1L Phosphinate.; Tetramethylene" do .do M 15. Dodecyl .....do Ethylene ..do MethyL. MethyL. 16. ..do ...do ..do Tertiary sulfonium Do. 17. HexadecyL... do Trimethylene.. Ammonium Methyl Meth 1. l8. ctadecyl ...do. Eth d Hydrogen... Ethy 19. do .do-... .do. Methyl--.

Eioosyl. do d 21 Dodecyl Phosphate Compounds wherein Z is phosphate' and X is ammonium wherein R and R are hydrogen and R is hydrogen, methyl, or ethyl (I) ROH P001. ROPCh+ 01 II II (II) ROPClz ClR OH HOP-O'R'Cl 1101 Compounds wherein Z is phosphate and X is ammonium wherein R is hydrogen and R and R are methyl or ethyl II (VI) Rolf-DRNR'R NaOH ll ea non-ornament N80] In these equations R and R are each methyl methyl, and neither of them is hydrogen. The alkyl dichlorophosphate in Reaction V can be made by the process of Reaction I hereinbefore. Reactions V and VI can be carried out under the following conditions:

Tempera- Solvent. ture, C. Time Reaction:

V Ethylenedichloride 25-40 2 hours to 4 hours. VI Methanol 25-30 15 mlns. to mins.

noi on gwmn H01 9 In Equation IV, R and R are each hydrogen, and R is hydrogeh, methyl, or ethyl. These reactions can be carried out' 'under the following conditions:

Compounds wherein Z is phosphate and X is quaternary ammonium ll 63 (VII) ROP-OR NHR'R R I NaOH In this equation R, R and R are each methyl pr ethyl, and none of them is hydrogen. The dialkylammonioalkyl alkylphosphate reactant in this equation can bejmade by Temperature, C.

Time

Solvent 2 hours to 4 hours.

0. mins. to 1 hour.

1 hour to 3 hours.

the process of Reaction VI. Reaction VII can be carried Compounds wherein Z is phosphonate and X is ammonium out under the following conditions: wherein R is hydrogen and R and R are methyl or Reaction VIL}; ethyl Solvent Diolr'ane.

Temperature Reflux (about 105 C. for dioxane). 5

Time l mills-45 mins. xv i c 0 i 4+ c ,c

0 Compounds wherein Z is phosphate and X is iL tertiary sulfonium in l H I 09 o e Ri -O R NHR'R +NaCl+H 00 The phosphate reactant in the equaiton of Reaction VIII i can be made by the process of Reaction III hereinbefore. Reaction VIII can be carried out under the following s commons In these equations R and R are each methyl or ethyl, Reaction VIII. and neither of them is hydrogen. The phosphonicdihalide Solvent Ethylene dichloride. reactant is Reaction XV can be made by the process of Temperature 50 C.l00 C. Reaction XI. Reactions-XV and XVI can be carried out Time l5 mins.2 hours. under the following conditions:

Compounds wherein Z is phosphonate and X is ammonium Compounds wherein Z isphosphonate and X is quaternary wherein R and R are hydrogen and R is hydrogen, ammonium methyl, or ethyl 011 In this equation R, R and R are each methyl or ethyl,

3/011 (5 and none of them is hydrogen. The dialkylammonioalkyl P0 O1 Poe 2H0 alkylphosphonate reactant in this equation can be made (x!) R +2 1BR T by the process of Reaction XVI. Reaction XVII can be OK carried out under the following conditions:

0 r E {L Reaction XVII. x11) R Ch+H0R C R C solvent Ethyl alcohoL 01 Temperature 50 C.- C.

Time 3-6 hours.

I OH Compounds wherein Z is phosphonate and X is tertiary sulfonium on o (xrv) Ri o rhcwnmmm-nio R NB R R +ECl E E 9 H 66 o xvm R -on -c1+nsno-n 6-0 n -s nuu+rrcr These reactions can be carried out under the following The phosphonate reactant in the equation of Reaction F conditions: XVIII can be made by the process of Reaction XIII here- I Tempera- Solvent .7 ture, C. Time Rea ti fX Excess trialkylphosphlte.. -150 4 hours to 8 hours. X N -270 iii mins. to 1 hour.

90-100 1 hour to 2 hours.

25-40 2 hours to 4 hours. 30-50 30mins. to 1 hour. 60-80 1 hour to 3 hours.

7 8 inbefore. Reaction XVIII can be carried out under the In this equation, the phosphinic acid reactant can be made following conditions: by the process of Reaction XXIV; R is hydrogen and R Reaction XVIII and R are each methyl or ethyl This reaction can be Solvent Ethyle'ne dichloride. carried out under the same conditlons as Reaction XXV. Temperature 50 C.-100 C. 5 Compounds wherein Z is phosphinate and X is Time -Q 15 mins.2 hours. quarternary ammonium Compounds wherein Z is phosphinate and X is ammonium Q wherein R and R are hydrogen and R is hydrogen, (XXVII) l methyl, or ethyl rum 0 d tert b l d O 0| 9 (XIX) 1 H +H# 0 :m Rl RINR2RSRI HBr.NR2R3RI I 2 atmospheres I 9 H 1 H 0 O In this equation, the reactant can be made by the process I l of Reaction XXIV, and R R and R are each methyl or (Xx) Rii '0Na+Hcl 'R ifloHFNacl ethyl, and none of them is hydrogen. This reaction can be H H carried out under the same conditions as Reaction XXV.

Compounds wherein Z is phosphinate and X is tertiary (xxx Rl|-OH cH,-N=N on sulfonrum (xxvnr al -on 2NaSR ELL-OCH: Nil H2O 1! i 0 (1; Elf-0N1: HSR5 NaBr (XXII) BIL-OCH! Na Rg-OCH: %H2T RISK 1 Na QI (I) 0 I H xxrx ni -0N8 Ru al -11 s mm NaI (XXIII) ROCH: IROH RP-OCH: NaI RISE 9 N89 310K The phosphinic reactant in Reaction XXVII can be made by the process of Reaction XXV hereinbefore. Reactions (XXIV) BI -OCH; 21113; XXVIII and XXII can be carried out under the following ROH conditions:

l 'rt Tl ill-0H cmBrt H20 Solvent Lmpem 115312;

40 Reaction: 0 XXVIII Dloxane 25-50 15-20 XXIX ..do 1 Reflux 1-10 (XXV) Ru-OH 1 101 C. for dioxane.

r The following examples illustrate the preparation of the lL ghvRm Bur-lu s compounds of this invention. Le EXAMPLE I In Equation XIX,;R' is an aliphatic radical containing Diisopropyl dodecylphosphonate was prepared by retwo less carbon atoms than the desired R. In Equation acting dodecyl bromide and triisopropyl phosphite accord- XXV, R and R are each hydrogen, arid R is hydrogen, ing to the technique described in Ford-Moore and Wilmethyl or ethyl. Reactions XIX-XXV can be carried out liams, Journal of the Chemical Society 1947, p. 1465. This under the following conditions: t reaction was carried out at a temperature of 145 C. and

. Tempera- Solvent ture, C. Time Reaction:

XIX Methanol 110-130 10-20 hours. XX Water/diethyl ether.- 20-35 Eminutes.

XXI Dlethyl ether 0-10 10-30 min t XXII.-- Toluene 26-30 3-5 hours. Reflux 1 2-4 hours. -60 Hhours. Reflux 1 '6-10 hours.

l About 10 C. for toluene. 1 About 56 6. tor acetone.

' Compounds whereipZis phosphinate andXis ammonium for a time period of 5 hours. The formed diisopropyl Whtfein is hydrogen and R3 and are methyl or dodecylphosphonate is converted to dodecylphosphonic ethyl acid using the pyrolytic method described in the copending 0 application of Roy, Ser. No. 218,863, filed Aug. 23, 1962 (XXVI) IL zNRzRR. and now abandoned. I

I 196 grams (0.78 mole) dodecylphosphonic acid was placed in a 1-liter flask. This flask was then placed on a steam bath. To this flask on the steam bath was added over a 15-minute period 360 grams (1.7 moles) PCl This addition was carried out under dry nitrogen. The formed mixture was maintained on the steam bath for one hour after the PCI,, addition was completed. During the PC], addition and thereafter the temperature of the mixture was maintained at 90-100 C. by the steam bath. The flask was then removed from the steam bath. The excess PC]; in the reaction mixture was then converted to POCl, by rapidly passing S0, into the reaction mixture for 90 minutes. The POCl, and SOCl, in the mixture were then removed from the mixture under vacuum, and the residue was distilled to yield 210 grams (0.73 mole) of substantially pure dodecylphosphonic dichloride, having a boiling point ranging from 117 C. to 119 C. at 0.1 mm. Hg.

400 ml. of triethylamine having been dried over CaSO; was then introduced into a 1-liter, S-neeked, round-bottom flask, equipped with a thermometer, a condenser protected with a drying tube, an addition funnel, and a mechanical stirrer. Then, 143.5 grams'(0.5 mole) of dodecylphosphonic dichloride was added to the flask'with stirring over a 45-minute period. Next, 44.5 grams (0.5 mole) of 2-dimethylaminoethanol was added to the flask dropwise with stirring over a 30-minute period. During the 2-dimethylaminoethanol addition period, the reaction mixture in the flask was maintained at 40-50 C. by cooling.

After addition of the Z-dimethylaminoethanol was completed, the reaction mixture in the flask was stirred for one additional hour at 45 C. The reaction mixture was then allowed to cool to room temperature.

To this reaction mixture at room temperature was added dropwise, with stirring, over a -minute period, 20 ml. (1.1 mole) of water. During the water addition, the temperature of the reaction mixture rose rapidly, and was maintained at about 60 C. by means of a cold water bath. After the 30-minute water addition period, 180 ml. of water was poured into the reaction mixture to effect complete solution of the reaction mixture.

To this solution was added 1 liter of water containing 60 grams (1.5 moles) of sodium hydroxide. This addition was carried out by pouring the sodium hydroxide solution into the reaction solution. The temperature of the formed solution was about C. during and after sodium hydroxide addition. The formed solution was evaporated on a steam bath under a current of nitrogen. The residue resulting from this evaporation was digested in 1 liter of boiling chloroform, and the insoluble materials were then removed by filtration. The chloroform was then evaporated on a steam bath under a current of nitrogen. The l60-gram residue was an extremely viscous, amber paste that was hygroscopic. This material was equilibrated with the atmosphere over a saturated solution of KSCN at room temperature yielding 172 grams of clear amber gel. Analysis of the gel showed it to be a mixture containing 90% by weight 2-(dimethylammonio)thyl dodecyl phosphonate, i.e., Compounds 9 in Table I hereinbefore, and 10% by weight water.

Into a 1-liter, 3-necked, round-bottom flask, equipped with a heating mantle, a reflux condenser, and a mechanical stirrer, was charged 110 grams of the above gel [0.34 mole 2-(dimethylammonio)ethyl dodecylphosphonate] dissolved in 500 ml. of denatured ethyl alcohol. To this solution was added 52.5 grams (0.37 mole) of methyl iodide. This addition was carried out over a 10-minute period. During this addition the formed mixture was maintained at a temperature of 60-70 C. After this addition, the mixture was brought to reflux temperature, i.e., about 78 C., and was stirred at reflux temperature for four hours. At this point, the reflux condenser was replaced with a distillation head and condenser, and 350 ml. of alcohol was removed by distillation. To the resulting mixture was added with Stirring 340 ml. of l N NaOH (0.34 mole NaOl-I). This addition was carried out all at once. During this addition the temperature of the mixture was maintained at 70-80 C. The solvent in the mixture was then evaporated on a steam bath. To the residue was added 1000 ml. water to form a reaction solution. This solution was mixed with about 0.5 equivalents of cation exchange resin in the hydrogen form and with about 0.5 equivalent of anion exchange resin in the hydroxide form. After about 30 minutes during which the mixture was periodically shaken, the resin was removed by filtration. The water in the filtrate was evaporated on a steam bath to provide an amber solid which was equilibrated over saturated KSCN solution at room temperature to yield 101 grams of clear, amber gel. Analysis of this gel showed it to be a mixture of 84% by weight Z-(trimethylammonio)ethyl dodecylphosphonate, i.e., Compound 7 in Table I hereinbefore, 11% by weight water, and 5% by weight sodium iodide.

2 (dimethylethylammonio)ethyl dodecylphosphonate can be prepared as above except that an equivalent amount of ethyl iodide is substituted for the methyl iodide above.

EXAMPLE II Into a 2-liter, stainless-steel autoclave were added 84 grams (0.5 mole) l-dodecene, 106 grams (1.0 mole) sodium hypophosphite monohydrate, 1 ml. di-tert.-butyl peroxide, and 350 ml. methanol. The autoclave was sealed, maintained at 120 C., and rocked for 17 hours. During this l7-hour period the pressure in the autoclave was 2 atmospheres. After this 17-hour period, the contents of the autoclave were allowed to cool to room temperature, after which the autoclave was opened and the contents removed. The contents were then diluted with 3 liters of distilled water, and then extracted three times, each time with 500 ml. of petroleum ether, and the extracts discarded.

Into the aqueous solution remaining was poured 100 ml. of concentrated hydrochloric acid. During this addition the temperature of the resulting mixture was approxi-' mately 35 C. The resulting mixture was extracted three times, each time with 500 ml. of petroleum ether, and the remaining aqueous phase was discarded. These ether extracts were dried over sodium sulfate, and the dried extracts were evaporated on a steam bath under nitrogen to yield 98 grams of crude dodecylphosphinic acid. Recrystallization from 300 ml. of petroleum ether gave 79 grams (0.34 mole) of substantially pure dodecylphosphinic acid.

70 grams (0.3 mole) of this substantially pure dodecylphosphinic acid is then dissolved in 200 ml. diethyl ether at 0 C. To this solution is added a diethyl ether solution of diazomethane prepared by adding 30 grams of N-nitrosomethylurea to a mixture of 75 ml. of 30% aqueous KOH and 250 ml. diethyl ether at 0-10 C., and decanting the ether layer from the aqueous layer prior to use. The diazomethane and dodecylphosphinic acid are reacted for 30 minutes at 010 C. The produced methyl dodecylphosphinate, 74 grams, is isolated by evaporating the diethyl ether and excess diazomethane on a steam bath under nitrogen.

72 grams (0.28 mole) of this methyl dodecylphosphinate is then dissolved in 250 ml. of toluene which has been dried over sodium ribbon. This solution is mixed with 6.5 grams (0.28 mole) sodium dispersed in 250 ml. toluene in a 1-liter, 3-necked, round-bottom flask,

equipped with addition funnel, thermometer, reflux condenser protected by a drying tube, and mechanical stirrer.

. The sodio derivative of the phosphinate is formed by to yield 93 grains of crude'2 bromoethyldodecylpiiosphinic acid.

- This crude 2-bromoethyldodecylphosphinic acid is dissolved in 200 ml. acetone. Into this solution is poured 60 grams (1 mole) of tri'methylamine. This mixture contained in a 500 ml. boiling flask surmounted with a reflux condenser is refluxed at about 56 C. for 8 hours. The resulting mixture is evaporated on a steam bath. The residue is dissolved in 200 ml. of methanol. This solution is shaken for 30 minutes with a mixture of 0.5 equivalent of cation exchange resin in the hydrogen form and 0.5 equivalent of anion exchange resin in the hydroxide form. The resins are then removed by filtration. The filtrate is evaporated to yield 85 grams of 2'(trimethylammonio)ethyl dodecylphosphinate, i.e., Compound in Table I hereinbefore.

2 (dimethylethylammonio)ethyl dodecylphosphinate and 2 (triethylammonio)ethyl dodecylphosphinate can be prepared as above except that dimethylethylamine and triethylamine, respectively, are substituted for the trimethylamine above. 3

In another case, 100 grams (0.3 mole) of 2-bromoethyldodecylphosphinic acid prepared as above is dissolved in 500 ml. of dioxane. To this solution is added 45 grams (0.64 mole) sodium methyl mercaptide. This 1 EXAMPLE III Into a l-liter, 3-necked flask, equipped with a thermometer, gas inlet tube, dropping funnel, and mechanical stirring assembly is placed 106 grams (0.69 mole) of POCl and 500 ml. of dry ethylenedichloride. To this formed solution, with stirring, is added dropwise over a 30-minute period 93 grams (0.5 mole) of l-dodecanol. During this addition, dry nitrogen is passed slowly through the stirred solution. The temperature of the solution starts out at room temperature, i.e., C., and rises about 5 C. during the dodecanol addition. Stirring is continued for 3 hours after addition is completed, during which the temperature of the reaction solution ranges from 25 C. to C. The excess POCl and'the ethylenedichloride are then removed by evaporation under water pump vauum using a 70 C. water bath to speed the evaporation. r

The residue from the evaporation, consisting of crude dodecyl dichlorophosphate, is dissolved in500 ml. of dry ,ethylene dichloride in apparatus identical with that described in the above paragraph. To this solution is added with stirring over a -minute period, '44 grams (0.5 mole) z-(dimethylaminmethanol. Stirring is continued for 2 hours after this addition. Dnringthe 2- (dimethylamino)ethanol addition period and'during the stirring thereafter the temperature of the reaction solution ranges from 25 C. to 30 C. The solvent is then removed by vacuum evaporation.

The residue from this evaporation is dissolved in 500 ml. of methanol containing 40 grams of NaOl-l and 50 ml. water. This solution is shaken from time to time during a thirty-minute period with a mixture of 1.5 equivalents of cation exchange resin in the hydrogen form and 1.5 equivalents of anion exchange resin in the hydroxide form. The resin is then removed by filtration. The solvent is then evaporated to yield 147 grams of 2- (dimethylammonio)ethyl dodecylphosphate, i.e., Cornpound 21in Table I above. 4 In another case, grams (0.3 mole) of Z-(dimethyla mm'onio)ethyl dodecylphosphate prepared as above is dissolved in 500 ml. of dioxane;' To this'solution is added over a 10-minute' period, 45 grams (0.32 mole) of methyl iodide. The mixture is then brough to reflux temperature, i.e., to about C., and is stirred at this temperature for 30 minutes. To the resulting mixture is added with stirriifg over a 5-minute period 300 ml. of 1 N NaOH (0.3 mole NaOH). The temperature of the mixture during this addition ranges from 100 C. to 72 C. The resulting mixture is purified by ion exchange to yield '94 grams of 2-(trimethylammonio)ethyl dodecylphosphate, i.e., Compound 2 in Table I hereinbefore.

Z-(dimethylethylammonio)ethyl dodecylphosphate can be prepared in the same manner as the Z-(trimethyiammonio)ethyl dodecylphosphate above except that an equivalent amount of ethyl iodide is substituted for the methyl iodide above. i Compounds'ofthis invention are useful per se as detergent and surface active agents. Desirably they are used with other materials to form detergent compositions, as for example, liquid, bar, tablet, granular or other compositions. Such detergent compositions can contain the reversed zwitterionics of this invention, and water-soluble inorganic alkaline builder salts', water-soluble organic alkaline sequestrant builder salts ormixtures thereof in a ratio of reversed zwitterionic to builder salt Of'about 4:1 to about 1:20. Such-detergent compositions ordinarily contain from 5% to 50% of detergent active and from 5% to 85% of builder salt. 1

Granular detergent compositions preferably contain about'5% to'about 50% of the reversed zwitterionics of this invention and liquid formulations preferably contain from about 2% to about 30% of such reversed zwitterionics. Granular'detergents preferably contain at least an equal amount of an alkaline builder saltpLiquid formulations preferably contain from about 5% to about 40% of a water-soluble alkaline builder salt, the balance of the composition being a solvent such as water, and/ or other liquid vehicles. Liquid formulations can also contain 'a hydrotroping electrolyte, e.g., sodium toluene sulfona'te. All percentages and parts herein are by weight unless specified otherwise.

Water-soluble inorganic alkaline builder salts wihch can be used in this invention alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Ammonium or substituted ammonium, e.g., triethanol ammonium, salts of these materials can also be used. Specific examples of suitable salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium and potassium pyrophosphate, sodium and ammonium bicarbonate, potassium triployphosphate, sodium hexaphosphate, sodium sesquicarbonate, sodium orthophosphate, and potassium bicarbonate' The preferred inorganic alkaline builders according to this invention are alkali metal tripolyphosphates for built granular and tablet compositions and alkali metal pyrophosphates for built liquid compositions. Potassium is the preferred alkali metal used in liquid compositions and sodium finds best application for granular or tablet compositions.

Examples of suitable organic alkaline sequestrant builder salts used in this invention alone or in admixture are alkali metal, ammonium or substituted ammonium, aminocarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(Z-hy- 13 droxyethyl)nitrilodiacetates, sodium and potassium nitrilotriacetates. Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as organic alkaline sequestrant builder salts (see US. Pat. 2,739,942). Also suitable as organic alkaline sequestrant builder salts are the water-soluble salts of polycarboxylate polymers and copolymers as described in the copending application of Francis L. Diehl Ser. No. 269,359, filed Apr. 1, 1963 and now US. Pat. 3,308,067 (e.g., polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene).

Polyphosphonates are also valuable builders in terms of the present invention, including specifically sodium and potassium salts of ethane-l-hydroxy-l,l-diphosphonic acid, sodium and potassium salts of methylene diphosphonic acid, sodium and potassium salts of ethylene diphosphonic acid, and sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Other examples include the alkali metal salts of ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-l,1,2-triphosphonic acid, ethane-Z-hydroxy-l,1,2-triphosphonic acid, propane- 1,1,3,3-tetraphosphonic acid, propane-l,l,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid.

Besides the builders being used together with the present reversed zwitterionics, it is also possible according to the present invention to use the reversed zwitterionic compounds of this invention in combination with other cleaning agents such as anionic, nonanionic, and other ampholytic and zwitterionic-organic detergent compounds. When it is desired to use such reversed zwitterionic compounds in combination with other detergent compounds, they are preferably utilized with anionic detergents because of the sudsing characteristics of the latter. The ratio of the reversed 'zwitterionic to such other detergent compound is from: about 10:1 to 1:5. If it is desired to use such a reversed zwitterionic in admixture with another detergent compound as the active portion of a cleaning composition, the ratio of such a mixture to the builder salt should he within the previously prescribed range of 4:1 to 1:20. A composition prepared along these lines can contain from 5% to 50% of such a mixture and 5% to 85% of a builder salt selected from water-soluble inorganic alkaliiie builder salts, water-soluble organic sequestrant buifder salts, and mixtures thereof, within the predescribed fatio range.

Examples anionic soap detergents which can be used in admixture with the reversed zwitterionic detergent, if desired, are the sodium, potassium, ammonium and. alkylolammonium salts of higher detergent range fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut: oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of suitable anionic organic non-soap detergents in the form of their watersoli rble salts are: alkylglycerylethersulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkylpolyethenoxy ether sulfates; acylsarcosinates; acyl esters of isethionates; N-acyl-N-methyl taurides; alkylbenzenesulfonates wherein the alkyl substituent is straight chain or branched chain; sulfonated alpha-olefins, e.g., such as described in the copending application of Kessler et al., Ser. No. 561,397, filed June 29, 1966; alkylphenol polyethenoxy sulfonates. In these compounds the alkyl and acyl groups, respectively, contain to 24 carbon atoms. They are used in the form of water-soluble salts, the sodium, potassium, ammonium, and alkylolammonium salts, for example. Specific examples are: sodium lauryl sulfate, sodium tallow alkyl sulfate; sodium salt of sulfonated alpha-tridecene; potassium N-methyl-N-lauroyl tauride; triethanolammonium tetrapropylbenzene sulfonate; sodium (linear) dodecyl benzene sulfonate.

Examples of nonionic organic detergents which can be used in the compositions of this invention, if desired, are: polyethylen efoxide condensates of alkylphenols wherein the alkyl group contains from 8 to 15 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkylphenol in the range of 8:1 to 20:1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products ranges froirr 5,000 to 11,000; the condensation products of from about 5 to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing frornS to 18 carbon atoms, e.g., condensation product of 6 moles of ethylene oxide with one mole of lauryl alcohol; higher alkyl dilower alkyl amine or phosphine oxides, e.g., dodecyldimethylamine' oxide or dodecyldimethyl phosphine oxide; alkyl methylsulfoxides such as dodecyl methyl sulfoxide.

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical carlr'be straight chain or branched and wherein one of the aliphatic substituents contains fromabout 10 to about 20 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate. Examples of compounds falling within this definition aresodium 3-dodecylaminopr'opionate, sodium 3 (N methyl-N-hexadecylamino)-2-hydroxypropane-lsulfonate and its dodecyl homolog, sodium 3-dodecylaminopropanel-sulfonate, sodium dodecyl beta-alanine, sodium N-alk'yl'taurines such as the one prepared by reacting dodecyl-amine with sodium isethionate according to the teaching of United States Letters Pat. No. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teachings of United States Letters Pat. No. 2,438,091, and the products sold under-the trade name Miranol" and described in United States Letters Pat. No. 2,528,378.

Zwitterionic" synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 10 to about 20 carbon atoms and one contains an anionic water solubilization group, e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate. Examples of compounds falling within this definition are: 3-(N,N dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate and the corresponding dodecyl and tetradecyl homologs and 3 (N,N dimethyl-N-dodecylammonio)-propane l sulfonate and the corresponding hexadecyl and tetradecyl homologs.

It is also possible according to the present invention to use the reversed zwitterionic detergent's in combination with anionic brighteners. A detergentfcomposition employing the combination of ingredients oidinarily can contain from about 0.01% by weight to about 2% by weight optical brightener. Examples of anionic optical brighteners which can be used herein are sodium 2-sulfo-4-(2- naphtho 1,2 triazolyl)stilbene and sodium 4,4'-bis(4- anilino-6-morpholino-s-triazo-2-ylamino)-2,2'-stilbene disulfonate.

The detergent compositions of this invention can also contain any of the usual adjuvants, diluents, and additives, for example, perfumes, antitarnishing agents, bacteriostatic agents, dyes, suds builders, suds depressors, and the like, without detracting from the advantageous properties of the composition.

The following examples illustrate detergent compositions containing the reversed zwitterionic compounds of this invention which can be used under conditions of ordinary usage to clean, for example, soiled clothing or dishes. All percentages herein are by weight unless otherwise specified.

15 EXAMPLE IV Solid-granules Percent 2-(trimethylammonio)ethyl dodecylphosphonate 17.5 Sodium tripolyphosphate 50.0 5 Sodium silicate (Na,O:SiO =l:2.5) 10.0 Sodium sulfate 17.5 Moisture 5.0

EXAMPLE v Compressed granulestablet 2-(trimethylammonio)ethyl dodecylphosphate 31.0; Tetrasodium pyrophosphate 52.0 Trisodium phosphate 10.0 Moisture 7.0

EXAMPLE VI 0 Solidgranules Percent 2-(trimethylammonio)ethyl dodecylphosphinate 32.0 Pentasodium ethane l hydroxy-1,1,2-triphosphonate 64.0 Moisture 4.0

EXAMPLE VII Solid-granules 3 (N ,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate 20.0 2-(dimethylsulfonio),ethyl dodecyclphosphinate 25.0 Sodium tripolyphosphate 35.0 Sodium carbonate 10.0 0 Sodium silicate (Na O:SiO;=1:2.5) 5.0 Moisture 5.0

EXAMPLE VIII Solid--granules 3-(trimethylammonio)propyl octadecylphosphonate 20.0 Sodium tallow alcohol sulfate 10.0 Trisodium ethane-l-hydroxy-l,l-diphosphonate 20.0 Sodium tripolyphosphate 10.0 Sodium nitrilotriacetate 10.0 Sodium sulfate 8.0 Sodium silicate (Na O:SiO,=1:2.5) 11.0 Moisture 11.0

EXAMPLE IX Liquid 2-(dimethylsulfonio)ethyl decylphosphonate 5.0 Sodium salt of S0 sulfonated 1:1 weight mixture of alpha-dodecene and alpha-tetradecene 10.0 Tetrapotassium pyrophosphate 19.0 Sodium silicate Na,o=si0,=1=1.6 3.8 Potassium toluene sulfonate 8.5 Carboxlmethyl hydroxyethyl cellulose .3 Water, balance. I

EXAMPLE X Liquid 2-(diethylsulfonioethyl decyclphosphate 6.0 Sodium (linear) dodecyl benzene sulfonate 6.0 Tetrapotassium propane-l,1,3,3-tetraphosphonate 20.0 Sodium silicate (Na;O:SiO- -=l:1.6) 3.8 Potassium toluene sulfonate 8.5 Carboxymethyl hydroxymethyl cellulose .3 Water, balance. 1

16 EXAMPLE XI Solid-granules Dodecyldimethyl phosphine oxide 5.0 Coconut oil soap 5,.0 Sodium tripolyphosphate 50.0 Tetrasodium ethylene'diamine tetraacetate 20.0

EXAMPLE XII Solid-granules Potassium dichloroisocyanurate 11.43 Sodium tallow fatty alcohol sulfate 11.0 Z-(trimethylammonio)ethyl dodecylphosphonate 5.0 Sodium tripolyphosphate 40.0 Trisodium phosphate 23.5 Sodium carboxymethylcellulose 0.36 Sodium silicate (SiO :Na- O ratio of 1.6:1) 6.0 Perfume 0.25 Sodium 2-sulfo-4-(2-naptho-l,2-trazolyl)stilbene 0.1

Moisture, balance.

It will be appreciated that the reversed zwitterionic compounds used in the present invention can be incorporated into many other liquid or granular detergent compositions with suitable adjustments being made in the other components.

Materials which are considered normal and desirable additives in liquid or granule detergent compositions can be added to the compositions of this invention without adversely affecting or modifying basic cleaning characteristics. For example, a tarnish inhibitor such as benzotriazole or ethylene thiourea may be added in amounts up to about 1%. Fluorescers, perfume, bleaching agents, color, antiredeposition agents, antibacterial agents, thickening agents, opacifiers, and blending or viscosity control agents, while not essential in the compositions of this invention, may also be added.

The compositions of the present invention can be used in conjunction with cool water washing situations as well as with warm and hot water.

What is claimed herein is:

1. A detergent composition consisting essentially of a reversed zwitterionic phosphorus compound having the formula R-ZR -X wherein R is selected from alkyl and alkenyl of from about 10 to about 20 carbon atoms; Z is a negatively charged radical selected from the group consisting of phosphate, phosphonate, and phosphinate radicals; R is an alkylene radical containing from 2 to about 4 carbon atoms; and X is a positively charged radical selected from the group consisting of ammonium and tertiary sulfonium radicals; said ammonium radical having the formula wherein R R and R are each selected from the group consisting of hydrogen, methyl, and ethyl; said tertiary sulfonium radical having the formula 63 age wherein R and R are each selected from the group consisting of methyl and ethyl; and a builder selected from the group consisting of water-soluble inorganic builder salts, water-soluble organic alkaline sequestrant builder salts and mixtures thereof, the weight ratio of said reversed zwitterionic phosphorus compound to said builder being in the range of about 4:1 to about 1:20.

2. The detergent composition of claim 1 wherein the reversed zwitterionic phosphorus compound is 2-(trimethylammonio)ethyl dodecylphosphonate.

3. The detergent composition of claim 1 wherein the reversed zwitterionic phosphorus compound is 2-(dimethylammonio)ethyl dodecylphosphonate.

4. A built detergent composition consisting essentially of about 5% to about 50% of a mixture of a reversed zwitterionic phosphorus compound having the formula RZR X wherein R is selected from alkyl and alkenyl of from about 10 to about 20 carbon atoms; Z is a negatively charged radical selected from the group consisting of phosphate, phosphonate, and phosphinate radicals; R is an alkylene radical containing from 2 to about 4 carbon atoms; and X is a positively charged radical selected from the group consistingof ammonium and tertiary sulfonium radicals; said ammonium radical having the formula wherein R, R and R are each selected from the group consisting of hydrogen, methyl, and ethyl; and an organic 18 anionic detergent; the ratio of the reversed zwitterionic detergent compound to said organic anionic detergent being in the range of 10:1 to 1:5 and from 5% to 85% of a builder material selected from the group consisting of water-soluble inorganic alkaline builder salts; water-soluble organic alkaline sequestrant builder salts; and mixtures thereof.

References Cited UNITED STATES PATENTS 3,507,937 4/1970 Zimmerer 252-152X LEON D. ROSDOL, Primary Examiner M. HALPERN, Assistant Examiner US. Cl. X.R. 

